Dihydronordicyclopentadienylsubstituted formals



Patented Feb. 18, 1947 DIHYDRONORDICYCLOPENTADIENYL- SUBSTITUTED FORMALSHerman A. Bruson, Philadelphia, Pa., assignor to The Resinous Products &Chemical Company, Philadelphia,- Pa., a corporation of Delaware .NoDrawing. Application March 9, 1944, v

Serial No. 525,757

1 Claim. (01. zoo-e11 V This invention relates to formals of alcoholscontaining a dihydronordicyclopentadienyl group and to a method for thepreparation of these formals from formaldehyde and said alcohols in thepresence of an acidic condensing agent.

The iormals of this invention are of the general formula CH2 CH CH2 CH2Cg CH I CH2 CE I CICH N Ge l CH2 CH-C-CH CH-CHI CH2 Thedihydronordicyclopentadienyl group,

CH1ais represented by the structure CaHl wherein CaH4 is a propenyl'enegroup which in conjunction with the adjoining carbon atoms forms acyclopenteno ring. The dihydronordicyclopentadienyl group is obtained inacid-cat 2 alyzed, addition-rearrangement, reactions fromdicyclopentadiene. It is monovalent and is attached to its addedsubstituent group, a, at a secondary carbon atom flanked, by a methylenegroup and a tertiary carbon atom in an endo-'- ethylene cyclopentanogroup carrying the propenylene group which forms a cyclopenteno grouptherewith.

The formals of greatest interest have the general formulaO10H1r-(OA),.-0'

wherein C1cI-I13- is the dihydronordicyclopenta di'enyl group, A is analkylene group of at least two carbon atoms, and n is zero or aninteger. A may also represent an alkylene group having a halogen or anether group as a substituent.

The formals of this invention are obtained "by condensing formaldehydein the presence or an acidic condensing agent with an alcohol containing the dihydronordicyclopentadienyl system.

Such alcohols are new compounds resulting from the additionrearrangement reaction. of (ii-.- cyclopentadiene with water orpolyhydri'c alcohols in the presence of sulfuric acid or other acidiccondensing agents, as described in my copending patent applicationsSerial Nos, 476,640 and 476,645, filed February 20, 1943, and now issuedas United States Patents Nos. 2,394,582 and 2,385,788, respectively. Aspolyhydric alcohols there may be used ethylene glycol, propylene glycol,trimethylene glycol, the various butylen glycols, and glycols havinglarger alkylene groups,

' polyalkylene glycols such as diethylene glycol,

triethylene glycol, tetraethylene glycol, dipropylene glycol,di-butylene glycol, and the like, or ethcrs of polyhydric alcohols withtwo free hydroxyl groups per molecule, or the polyhydric alcoholsthemselves with more than two hydroxyl groups. Typicaldihydronordicyclopentadienyl-containing alcohols which are useful forthe preparation offormals of this invention are, by way of exa ple, thefollowing:

4 q 7 sodium hydroxide solution'followed by a water wash, dried, anddistilled. Benzene was first re- Froni dicyclopentadiene and- Thecondensation of formaldehyde with any 25 moved unchangedhydroxydihydronordicyclopentadiene of these alcohols containing adihydronordioyclopentadienyl group takes place readily at 50"--'150.

C. or somewhat higher by heating a mixture of; formaldehyde'with thealcohol in the presence of an acidic condensing agent. The reactants arepreferably mixed in a'ratio of about one mol of formaldehyde to two molsof the alcohol, but excess of either reactant is permissible.

Typical of the acidic condensing agents which may be used are phosphoricacid, sulfuric acid, hydrochloric acid, dihydroxyfiuoboric acid, acidicsiliceous clays, benzene sulfonic acid, zinc chlo-' ride,phosphotung'stic acid, and the like. The quantity of acidic condensingagents used is small, an amount from 0.5% to 5 of the weight of thereactants being usually suflicient for the purpose;

Water is evolved and is advantageously removed by utilizing an organicsolvent, such as benzene or toluene, to help distill off the water in anazeotropic mixture as fast as it is formed. In place of benzene theremay be used other inert solvents, including hydrocarbons, such astoluene and xylene, ethers such as propyl or butyl ethers', chlorinatedsolvents such as dichloroor tetrachloro-ethane, and the like.

After the reaction is complete, the crude product is neutralized withalkali and the product isolated by vacuum distillation, by steam-vacuumdistillation, or simply by stripping oil the solvent and low boilingimpurities with subsequent clarification or bleaching of the residualhigh-boiling product.

Theformals obtained are high-boiling oils or low-melting solids yieldingviscous, oily liquids of particular value for the preparation ofautoxidizable coatings.

The following examples illustrate thisinvention, it being understoodthat the paraformaldehyde can be replaced with trioxymethylene oraqueous formaldehyde. 7 i

A mixture of 300 g. of hydroxydihydronordicyclopentadiene, 30 g. ofparaformaldehyde, 200 g. of benzene, and 10 g. of syrupy 85% phosphoricacid was stirred and boiled under a reflux con denser attached to awater trap for 85 minutes, during which time g. of water collected inthe trap. The product was washed with excess dilute and then underreduced pressure was taken off in an amount of 52 g. The desired formaldistilled over between 183 and 203 C. at 1.5-3 mm. as a colorless oil.The yield was 215 g. Upon redistillation it boiled at 180 C.

at 2 mm.

The hydroxydihydronordicyclopentadienyl formal thus obtained polymerizesto a colorless, very viscous oil when heated at 100C. with 5%by Weightof benzoyl peroxide' This polymer as well as the unpolymerized formaldries by autoxidation upon exposure to the air, alone or withsiccatives, to a colorless varnish-like film. It can also be blendedwith drying oils such as linseed oil to yield high quality varnishes andbaking enamels. 1

Example .2

CroHm-O-CHzCHz-O I v 7 CH2 C1cH13--0-CHaOH2-O A mixture consisting of291 g. of beta-hydroxyethoxydihydronordicyclopentadiene,

together with 200 g. of benzene, 30 g. of paraformaldehyde, and 10 g. ofphosphoric acid was stirred and boiled under a reflux condenser attachedto a water trap for three hours at 85-93 C. until 20 g. of water hadcollected in the trap. The product was washed with dilute sodiumhydroxide solution to remove the catalyst, and the washed productevaporated to dryness to recover the solvent. The residual oil wasdistilled in vacuo.

The di-(dihydronordicyclopentadienyloxyethyl) formal distilled over at235-245 C./1.5 mm. as an almost colorless oil. The yield was 212 g.About 57 g. of unchanged ether alcohol was recovered.

Example 3 anemic and the benzene distilled off from the clear filtrate.The residual oil upon Y distillation in vacuo yielded 253 g. ofdi-(dihydronordicyclopentadienyl) formal boiling between 180? and 2002C.9/02 I mm., identicalwith that of Example 1. I I l 5 .mExample' ownu-ocmcm-o cmons-o an almost colorless oil at, 285 C./2 mm. The yield was 85g.

Example 5 CmHn-O-CHzCHzCHz-O C10HlaO--CHzCH2CH2-O A mixture consistingof 208 g. of gamma-hydroxypropyloxydihydronordicyclopentadiene, 3O

24 g. of paraformaldehyde, 150 g. of benzene and 20 g. of acid Tonsilclay was boiled under a reflux condenser until 12 cc. of water hadcollected in a trap attached thereto. This required two hours. Thereaction mixture was filtered to remove the clay and the filtrateevaporated to dryness. The residual oil was distilled in vacuo at 2.5mm. pressure. The fraction boiling at 260- 270 C./2.5 mm. was thedesired formal. The 40 yield was 165 g. It is a colorless oil.

Example 6 A mixture of 104 g. of glyceryl-alpha-methylgamma(dihydronordicyclopentadienyl) ether, 15 g. of trioxymethylene, 100 g.of benzene, and. 10 g. of acid Tonsil clay was boiled under a refluxcondenser attached to a trap until no more water distilled over. Thisrequired about two hours. The clay was filtered off and the filtratedistilled first to remove the solvent and then under reduced pressure-to purify the desired product.

The formal having the formula CHr-O-CHr-lH-CHrO-CwHn distilled over at267-274 C./2.5 mm. as a colorless oil.

In a similar manner the following formals are obtained as thick oilsfrom the corresponding a1- cohols in the list given above.

CH2 O CruHm-O-CHz-CHP-CHr-O-CroHm The above compounds, when blown withair at 0., go over to extremely viscous oils and resins which absorboxygenfrom the air. They have the unique property of drying in air byabscrption of oxygen, behaving in this respect like the natural dryingoils, such as linseed oil or tun oil. They also polymerize to viscousoils useful as varnishes either alone 01' when blended or copolymerizedwith drying oils, alkyd resins, or

other resins. They may be mixed with vinyl and acrylic compounds whichare then polymerized. They may be used not only for paints, varnishes,

and lacquers but also as bonding materials for cork and fibres, as forthe preparation of linoleum, molding compositions, laminated fabrics,and the like. i

I claim:

As a new compound, the formal of hydroxydihydronordicyclopentadiene, analcohol obtained by the acid-catalyzed, addition-rearrangement reactionof water and dicyclopentadiene and further characterized by attachmentof its hydroxyl group to a secondary carbon atom flanked by a methylenegroup and a tertiary carbon atom in '7 anendoethylene cyclbpentano groupwhich forms a cyclopenteno group therewith.

file of this patent: 2,385,788

7 UNITED STATES PATENTS MA .BR Number Name v I Date 7 2,036,304 Seymour'AprQ '7,'193V6 REFERENCES T M 2,183,317 Auden Dec; 12,1939 ,Thefollowing references are of record in the 7 2,394,582 Bruson' Feb. 12,1946 Bruson Oct, 2, 1945

